Determination of nanomole quantities of lower aldehydes by cold-vapour atomic absorption spectrometry

A method is described for the determination of 10–100 nmole of methanal and 20–150 nmole of ethanal and propanal. The method is based on the oxidation of aldehydes to the corresponding acids by mercuric ion which in turn is reduced to elemental mercury, followed by cold-vapour atomic absorption spectrometry. Calibration plots were constructed between the concentration of each aldehyde and absorbance, while the calibration from the conventional cold vapour procedure was used for total aldehydes determination. The method is selective and can be used for aldehyde determination in the presence of ketones, acetals, alcohols, acids, esters, ethers, organic chlorides and epoxides. This simple method is characterised by 98–102% recoveries and standard deviations of 3%.     

ESR spectra of the OD radical in the 2Π32, J = 32 state, v = 0–5 levels

The paramagnetic resonance absorption spectrum of the OD radical in the excited vibrational levels up to v = 5 of the ground ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$, $\text{J =}\text{3}\text{2}$ state has been observed at X-band frequencies. The theory of the Zeeman effect of a paramagnetic ²Π state of a light diatomic molecule has been applied to analyze the spectrum. The Λ-doubling frequencies, the molecular g factors, coefficients of the second order Zeeman effect, and the hyperfine interaction constants were determined for each of the vibrational levels. The experimental results agree reasonably well with the values calculated from (a) optical data and (b) ab initio data. The experimental determinations are still much better than theoretical calculations.     

A novel three carbon-amino grignard reagent: its use in an efficient pyrrolidine synthesis

A novel primary amino protected Grignard reagent has been developed; 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-propyl magnesium bromide 1a. Its usefulness is illustrated in the synthesis of 2-substituted pyrrolidines.     

Isolation of onosmins A and B, lipoxygenase inhibitors from Onosma hispida

Onosmins A (1) and B (2), lipoxygenase inhibitors, have been isolated from Onosma hispida. Their structures were established as 2-[(4-methylbenzyl)amino]benzoic acid (1) and methyl 2-[(4-methylbenzyl)amino]benzoate (2) through spectroscopic studies, including 2D-NMR. The known compounds apigenin (3), 6,4'-dimethoxy-3,5,7-trihydroxyflavone (4), 6,7-dimethoxy-3,5,4'-trihydroxyflavone (5) and apigenin 7-O-beta-D-glucoside (6) are also reported for the first time from this species. Compounds (1) and (2) inhibited lipoxygenase (LOX, EC 1.13.11.12) enzyme in a concentration-dependent fashion with IC50 values of 24.0 and 36.2 microM, respectively. Lineweaver-Burk as well as Dixon plots and their secondary replots indicated that the nature of inhibition was purely a non-competitive type, with K(i) values 22.0 microM and 31.1, respectively.     

On the total energy of two-electron atoms

Using the Multi-Configuration Dirac-Fock (MCDF) method we calculate with 9 configuration state functions the correlation energy as well as the total energy of the lowestJ=0 ground state of all two-electron systems from H^? to Thorium (Z=90). A comparison with experimental data, which are available only in the lowZ region, shows a very good agreement.     

Experimental/theoretical electrostatic properties of a styrylquinoline-type HIV-1 integrase inhibitor and its progenitors

We have established that polyhydroxylated styrylquinolines are potent inhibitors of HIV-1 integrase (IN). Among them, we have identified (E)-8-hydroxy-2-[2-(4,5-dihydroxy-3-methoxyphenyl)-ethenyl]-7-quinolinecarboxylic acid (1) as a promising lead. Previous molecular dynamics simulations and docking procedures have shown that the inhibitory activity involves one or two metal cations (Mg2+), which are present in the vicinity of the active center of the enzyme. However, such methods are generally based on a force-field approach and still remain not as reliable as ab initio calculations with extended basis sets on the whole system. To go further in this area, the aim of the present study was to evaluate the predictive ability of the electron density and electrostatic properties in the structure-activity relationships of this class of HIV-1 antiviral drugs. The electron properties of the two chemical progenitors of 1 were derived from both high-resolution X-ray diffraction experiments and ab initio calculations. The twinning phenomenon and solvent disorder were observed during the crystal structure determination of 1. Molecule 1 exhibits a planar s-trans conformation, and a zwitterionic form in the crystalline state is obtained. This geometry was used for ab initio calculations, which were performed to characterize the electronic properties of 1. The electron densities, electrostatic potentials, and atomic charges of 1 and its progenitors are here compared and analyzed. The experimental and theoretical deformation density bond peaks are very comparable for the two progenitors. However, the experimental electrostatic potential is strongly affected by the crystal field and cannot straightforwardly be used as a predictive index. The weak difference in the theoretical electron densities between 1 and its progenitors reveals that each component of 1 conserves its intrinsic properties, an assumption reinforced by a 13C NMR study. This is also shown through an excellent correlation of the atomic charges for the common fragments. The electrostatic potential minima in zwitterionic and nonzwitterionic forms of 1 are discussed in relation with the localization of possible metal chelation sites.     

Mechanism and substrate stereochemistry of 2-amino-3-oxobutyrate CoA ligase: implications for 5-aminolevulinate synthase and related enzymes

The condensation process catalysed by 2-amino-3-oxobutyrate CoA ligase (KBL; also known as 2-amino-3-ketobutyrate ligase) involves the loss of the pro-R hydrogen atom of glycine and occurs with the inversion of stereochemistry; a similar scenario is envisaged for the condensation step of other alpha-oxoamine synthases.     

Interacting Entropy-Corrected Holographic Chaplygin Gas Model

Holographic dark energy (HDE), presents a dynamical view of dark energy which is consistent with the observational data and has a solid theoretical background. Its definition follows from the entropy-area relation S(A), where S and A are entropy and area respectively. In the framework of loop quantum gravity, a modified definition of HDE called “entropy-corrected holographic dark energy” (ECHDE) has been proposed recently to explain dark energy with the help of quantum corrections to the entropy-area relation. Using this new definition, we establish a correspondence between modified variable Chaplygin gas, new modified Chaplygin gas and the viscous generalized Chaplygin gas with the entropy corrected holographic dark energy and reconstruct the corresponding scalar potentials which describe the dynamics of the scalar field.     

On the index of powers of edge ideals

The index of a graded ideal measures the number of linear steps in the graded minimal free resolution of the ideal. In this paper, we study the index of powers and squarefree powers of edge ideals. Our results indicate that the index as a function of the power of an edge ideal I is strictly increasing if I is linearly presented. Examples show that this needs not to be the case for monomial ideals generated in degree greater than two.